JP2000143786A - Charge-transfer polyester and organic electronic device produced by using the polyester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a charge-transfer polyester having high performance, producible easily and useful as an electrophotographic receptor by including respectively specific dicarboxylic acid component and diol component as partial structures. SOLUTION: The objective polyester contains (A) at least one kind of structure expressed by CO-(T)a-A-(T)a-CO as a dicarboxylic acid component and (B) at least one kind of structure expressed by O-(T)b-A'-(T)b-O A and A' are each a bivalent group of formula [R1 to R3 are each H, a halogen, an alkyl or the like; X is a (substituted)bivalent organic group; (a), (b), (k) and (m) are each 0 or 1; T is a 1-10C bivalent hydrocarbon group]} as partial structure of each repeating unit. The above polyester preferably has a weight-average molecular weight of 10,000-300,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel charge transporting polyester and an organic electronic device using the same, particularly to an electrophotographic photoreceptor.

[0002]

2. Description of the Related Art Charge transporting polymers typified by polyvinyl carbazole (PVK) are known as photoconductive materials for electrophotographic photoreceptors, and the 36th JSAP Conference on Applied Physics, 31p-K-12 (1990). And the like, it is promising as an organic electroluminescent device material. These materials form a layer together and are used as a charge transport layer. As a material for forming the charge transport layer, PVK is used.
And a low molecular weight dispersion in which a low molecular weight compound having a charge transporting property is dispersed in a polymer are well known. In general, a low-molecular charge transporting material is deposited and used as an organic electroluminescent element. Of these, the low molecular dispersion type has become mainstream, particularly for electrophotographic photoreceptors, because it has a variety of materials and it is easy to obtain high-performance ones.

[0003] In recent years, electrophotographic photoconductors have been used in high-speed copiers and printers as organic photoconductors have become more sophisticated. When used in a printer, the current performance is not always sufficient, and a particularly long life is desired. One of the important factors that determines the life of an organic photoreceptor is the wear of the surface layer. Current organic photoreceptors
The so-called layered type in which a charge transport layer is laminated on a charge generation layer is predominant, and therefore the charge transport layer is often a surface layer. At present, the low-molecular-weight dispersion transporting layer, which is the mainstream, is being obtained with satisfactory performance in terms of electrical properties.However, since low-molecular compounds are dispersed in a binder resin and used, The inherent mechanical performance of the resin is reduced, and the wear is essentially weak. In contrast, charge-transporting polymers have the potential to significantly improve the above disadvantages,
Currently being actively studied. For example, U.S. Pat.
No. 806,443 discloses polycarbonates by polymerization of certain dihydroxyarylamines with bischloroformate and is disclosed in U.S. Pat.
No. 6,444 discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine and phosgene. U.S. Pat. No. 4,801,517 discloses a polycarbonate obtained by polymerizing a bishydroxyalkylarylamine with bischloroformate or phosgene.
No. 165 and U.S. Pat. No. 4,959,288 describe polycarbonates by polymerization of certain dihydroxyarylamines or bishydroxyalkylarylamines with bischloroformates, and by polymerization with bisacyl halides. Polyesters are disclosed. Further, U.S. Pat. No. 5,034,296 discloses arylamine polycarbonates and polyesters having a specific fluorene skeleton, and U.S. Pat. No. 4,983,482 discloses polyurethane. ing. Furthermore, Japanese Patent Publication No. 59-289
03 discloses a polyester having a specific bisstyrylbisarylamine as a main chain. Also, JP-A-61-20953, JP-A-1-134456, JP-A-1-134457, and JP-A-1-134
462, JP-A-4-1330065, JP-A-4-133066, and the like propose a polymer having a pendant charge-transporting substituent such as hydrazone or triarylamine and a photoreceptor using the same. Have been. In particular, a polymer having a tetraarylbenzidine skeleton is referred to as "The Sixth International."
al Congress on Advances i
n Non-impact Printing Tec
hnologies. 306, (1990) ", it has high mobility and high practicality.

[0004]

By the way, the charge transporting polymer is required to have various properties such as solubility, mobility, and matching of oxidation potential. In order to satisfy these requirements, a substituent is introduced. It is common to control physical properties. Since the ionization potential of the charge transporting polymer is almost determined by the charge transporting monomer, it is important to be able to control the ionization potential of the charge transporting monomer. Monomers that are the raw materials for the above-mentioned triarylamine polymers can be broadly classified into two types: dihydroxyarylamines and bishydroxyalkylarylamines.
However, since dihydroxyarylamine has an aminophenol structure, it is easily oxidized and is difficult to purify. In particular, in the case of a parahydroxy-substituted structure, it becomes more unstable, but it is difficult to change the position of the substituent and control the ionization potential. Further, since the aromatic ring has a structure in which oxygen is directly substituted, the electron distribution tends to cause a bias in the charge distribution and the mobility tends to decrease. On the other hand, bishydroxyalkylarylamines have no effect on the electron-withdrawing property of oxygen due to the methylene group, but it is difficult to synthesize monomers. That is, in the case of synthesizing by reacting diarylamine or diarylbenzidine with 3-bromoiodobenzene, since both bromine and iodine are reactive, the product is likely to be a mixture, resulting in a decrease in yield. In addition, there is a problem that alkyl lithium and ethylene oxide used for lithiation of bromine compounds have high danger and toxicity, and require careful handling.

In order to solve this problem, the present inventors have made intensive studies on a charge transporting polymer, and as a result, have found that JP-A-8-253568 and JP-A-8-21640.
JP-A-8-208820 and JP-A-9-208820
No. 110974 discloses a novel high performance charge transporting polymer. What is described in these publications is an alternating copolymerized charge transporting polymer represented by the following general formula (III) or (IV). H- (O-Y) _r- O [CO-A-CO-O- (YO) _r ] _p- H (III) B- [CO-A-CO-O- (YO) _r- —CO—Z—CO—O— (YO) _r ] CO—A—CO—B ′ (IV) wherein Y and Z each represent a divalent hydrocarbon group; Represents a divalent group represented by the formula,

Embedded image (R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
X represents a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent organic group. a, b, k and m each represent an integer of 0 or 1, and T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched. B and B ′ each independently represent a group —O— (YO) _r
—H or a group —O— (YO) _r —CO—Z—CO—O
R '(where R' represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group; Y and Z each represent a divalent hydrocarbon group; Represents an integer of 1 to 5), and r represents 1
Represents an integer of 5 to 5, and p represents an integer of 5 to 5000. ]

Although this charge transporting polymer has excellent properties as compared with conventional ones and has high practicability, it is not sufficient for the demand for higher speed.
As a result of studying this point, in the charge transporting polymer of the alternating copolymerization represented by the general formulas (III) and (IV), the portion responsible for charge transport is only the portion of the group A, and the charge transport function It has been found that the demand for higher speed cannot be met because the ratio of the portion (the portion of group A) decreases.
That is, it is well known that the charge transport ability of a low-molecular charge transport material increases as the concentration in the charge transport layer increases. By doing so, it is considered that higher functionality can be achieved. However, since it is difficult to control the availability of the monomer used as the raw material of the polymer, or the polymerization method and the polymerization conditions, for example, even to a portion corresponding to the groups Y, B and B 'in the general formula (III) or (IV). Polymers incorporating a charge transport moiety have not been studied.

Accordingly, it is an object of the present invention to provide a novel high-performance charge-transporting polyester which is easy to produce. Another object of the present invention is to provide an organic electronic device, particularly an electrophotographic photosensitive member, using the charge transporting polyester.

[0008]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the reduction of a monomer having a partial structure of a dicarboxylic acid component represented by the following general formula (I) facilitates the reduction. It is possible to synthesize a monomer having a partial structure of a diol component represented by the following general formula (II),
Using these monomers, at least one or more of the structures represented by the following general formula (I) and at least one or more of the structures represented by the following general formula (II) are contained as a partial structure of a repeating unit. As a result, it has been found that a high-performance charge-transporting polyester resin can be synthesized, and the present invention has been completed.

Therefore, the charge-transporting polyester of the present invention is represented by at least one of the structures represented by the following general formula (I) as a dicarboxylic acid component and represented by the following general formula (II) as a diol component. At least one of the structures
Or more as a partial structure of a repeating unit, and the weight average molecular weight is preferably 10,000 to 300,000. -CO- (T) a-A- (T) a-CO- (I) -O- (T) b-A '-(T) b-O- (II) wherein A and A' are And a divalent group represented by the following formula.

[0010]

Embedded image (R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
X represents a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent organic group. a, b, k and m each represent an integer of 0 or 1, and T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched. The organic electronic device of the present invention is characterized in that the charge transporting polyester is contained in a charge transporting functional film, and is preferably an electrophotographic photosensitive member having a photosensitive layer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formulas (I) and (II), specific structural examples of T are shown below. The arylamine skeleton may be attached to either side, for example,
T-2r indicates that the arylamine skeleton is bonded to the right side of the structure T-2, and T-21 indicates that the arylamine skeleton is bonded to the left side of the structure T-2.

[0012]

Embedded image

[0013]

Embedded image

Examples of the group X include those selected from the following groups (1) to (7).

Embedded image

[In the formula, R ₄ is a hydrogen atom, a carbon number of 1 to 4;
Represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, and R _{5 to} R ₁₀ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl group, or a halogen atom;
Or means 1. Further, the group V includes the following groups (8) to
Shows the one selected from (17).

[0016]

Embedded image (In the formula, d means an integer of 1 to 10, e is 1 to 3
Means an integer. )]

Examples of the structures represented by the above general formulas (I) and (II) are shown in Tables 1 to 7 and Tables 8 to 14, respectively. The polyester in the present invention is not limited thereto. is not. (Specific examples of general formula (I))

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

(Specific examples of general formula (II))

[Table 8]

[0025]

[Table 9]

[0026]

[Table 10]

[0027]

[Table 11]

[0028]

[Table 12]

[0029]

[Table 13]

[0030]

[Table 14]

The monomer serving as the dicarboxylic acid component used in the production of the charge transporting polymer of the present invention can be easily synthesized by reacting an arylamine or diarylbenzidine or the like with a halogenated carboalkoxyalkylbenzene. Further, the diol component can be synthesized by reducing the obtained monomer to be a dicarboxylic acid component using lithium aluminum hydride, sodium borohydride, or the like.

For the synthesis of a charge transporting material having an alkylene carboxylic acid ester group, see JP-A-5-80550.
Japanese Patent Application Laid-Open Publication No. H11-157, describes a method of introducing a chloromethyl group, forming a Grignard reagent with Mg, converting the carboxylic acid to carboxylic acid with carbon dioxide, and then esterifying the carboxylic acid. However, in this method, chloromethyl groups cannot be introduced from an early stage of raw materials due to high reactivity of the chloromethyl groups. Therefore, after forming a skeleton such as triarylamine or tetraarylbenzidine, for example, a methyl group introduced at an early stage of the raw material is converted into a chloromethyl group, or an unsubstituted one is used at the raw material stage. It is necessary to convert directly to chloromethyl, or to introduce a formyl group and reduce it to a hydroxymethyl group, and then to convert it to a chloromethyl group with thionyl chloride or the like. However, charge-transporting materials having a skeleton such as triarylamine and tetraarylbenzidine are very reactive, so that a substitution reaction to an aromatic ring easily occurs. Therefore, the introduced methyl group is converted to a chloromethyl group. It is virtually impossible to convert to Further, in the raw material stage, in the method of directly using chloromethylation by using an unsubstituted chloromethyl group, a chloromethyl group can be introduced only at the para-position to the nitrogen atom. Further, the method of introducing a formyl group and then leading to a chloromethyl group has a problem that the reaction step is long. In contrast, the method of reacting an arylamine or diarylbenzidine or the like with a halogenated carboalkoxyalkylbenzene to obtain a monomer is excellent in that it is easy to change the position of the substituent and control the ionization potential. This method makes it possible to control the ionization potential of the charge transporting polymer. Since the charge transporting monomer used in the present invention can easily introduce various substituents and is chemically stable,
It is easy to handle and improves the above-mentioned problems.

The charge transporting polyester resin of the present invention comprises
Using at least one or more of the monomers represented by the following general formula (V) and at least one or more of the monomers represented by the following general formula (VI), for example,
It can be synthesized by polymerizing according to the method described in Vol. When performing synthesis using a plurality of monomers, in order to control the polymerization reaction and increase the molecular weight, all monomers having a partial structure of a dicarboxylic acid component, and all monomers having a partial structure of a diol component, It is preferable that the functional groups be the same. For example, if the functional group is a methyl ester group, it is preferable to use one in which all monomers have a methyl ester group.

E-CO- (T) a-A- (T) a-CO-E (V) HO- (T) b-A '-(T) b-OH (VI) A ′, T, a and b have the same meanings as described above, respectively, E represents a hydroxyl group, a halogen atom,
Or a group -OR ₁₁ . (However, R ₁₁ represents an alkyl group, a substituted or unsubstituted aryl group, or an aralkyl group.)]

Next, the synthesis of the charge transporting polyester of the present invention will be described. The charge-transporting polyester may be synthesized from only the monomer represented by the general formula (V) and the monomer represented by the general formula (VI). A monomer having no charge transport component other than the monomers represented by the above general formulas (V) and (VI) may be used in combination. Examples of the monomer having no charge transport component include those represented by the following formula. E-CO-R
_{12 -CO-E (VII) HO} -R 13 -OH (VIII) ( wherein, E is has the same meanings as defined above, R ₁₂ represents an alkylene group or a divalent aromatic radical, R ₁₃ represents an alkylene group or a divalent aromatic group that may be bonded via an oxygen atom.) When these monomers are used, the following structure is included in the partial structure of the repeating unit become. If these monomers are used, their content is 50% by weight
Or less, more preferably 30% by weight or less.

—CO—R ₁₂ —CO— (IX) —O—R ₁₃ —O— (X) Specifically, isophthalic acid,
Terephthalic acid, adipic acid, their acid chlorides and bismethyl esters can be used, and as the diol component, ethylene glycol, propylene glycol, diethylene glycol, bisphenol and the like can be used.

(1) When E is a hydroxyl group When E is a hydroxyl group, a diol component monomer and a dicarboxylic acid component monomer are mixed in substantially equivalent amounts and polymerized using an acid catalyst. As the acid catalyst, those used in ordinary esterification reactions such as sulfuric acid, toluenesulfonic acid, and trifluoroacetic acid can be used. 1/10000 to 1/10 parts by weight, preferably 1 / 10,000 parts by weight, per 1 part by weight of the dicarboxylic acid component monomer is preferable. Is used in the range of 1/1000 to 1/50 parts by weight. In order to remove water generated during the polymerization, it is preferable to use a solvent that can be azeotropic with water, and toluene, chlorobenzene, 1-chloronaphthalene, and the like are effective, and based on 1 part by weight of the generated polymer, 1 to 100 parts by weight,
Preferably it is used in the range of 2 to 50 parts by weight. The reaction temperature can be arbitrarily set, but the reaction is preferably performed at the boiling point of the solvent in order to remove water generated during the polymerization.

After completion of the reaction, if no solvent is used, the solvent is dissolved in a soluble solvent. When a solvent is used, the reaction solution is directly dropped into a poor solvent in which alcohol such as methanol and ethanol or a polyester such as acetone is difficult to dissolve, thereby precipitating a charge-transporting polymer and forming a charge-transporting polyester. After separation, it is sufficiently washed with water or an organic solvent and dried. Further, if necessary, the re-precipitation treatment of dissolving in a suitable organic solvent and dropping it into a poor solvent to precipitate a charge transporting polyester may be repeated. In the case of the reprecipitation treatment, it is preferable to carry out the stirring with a mechanical stirrer or the like while efficiently stirring. The solvent for dissolving the charge transporting polyester in the reprecipitation treatment is 1 to 1 part by weight based on 1 part by weight of the produced polyester.
It is used in an amount of 00 parts by weight, preferably 2 to 50 parts by weight. The poor solvent is used in an amount of 1 to 1000 parts by weight, preferably 10 to 50 parts by weight, based on 1 part by weight of the produced polyester.
It is used in the range of 0 parts by weight.

(2) When E is a Halogen When E is a halogen, a diol component monomer is mixed with a dicarboxylic acid component monomer in substantially equivalent amounts, and polymerized using an organic basic catalyst such as pyridine or triethylamine. The organic basic catalyst is one of the dicarboxylic acid component monomers.
It is used in 1 to 10 equivalents, preferably 2 to 5 equivalents, relative to the equivalent. As the solvent, methylene chloride, tetrahydrofuran (THF), toluene, chlorobenzene, 1-
Chloronaphthalene is effective, and is used in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight based on 1 part by weight of the produced polyester. The reaction temperature can be set arbitrarily. After the polymerization, reprecipitation treatment and purification are performed as described above.

In the case of a highly acidic dihydric alcohol such as bisphenol, an interfacial polymerization method can also be used. That is, polymerization can be carried out by adding a diol component monomer to water, adding an equivalent or more of a base and dissolving it, and then adding a solution of the diol component monomer and an equivalent amount of a dicarboxylic acid component monomer with vigorous stirring. At this time, water is used in an amount of 1 to 1000 parts by weight, preferably 2 to 500 parts by weight, based on 1 part by weight of the diol component monomer. Solvents for dissolving the dicarboxylic acid component monomer include methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene,
-Chloronaphthalene is effective. The reaction temperature can be set arbitrarily, and it is effective to use a phase transfer catalyst such as an ammonium salt or a sulfonium salt to promote the reaction. The phase transfer catalyst is composed of one of the dicarboxylic acid component monomers.
0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per part by weight.
It is used in the range of 2 to 5 parts by weight.

(3) When E is -OR ₁₁ When E is -OR ₁₁ , when the diol component monomer is substantially non-volatile, the diol component monomer is substantially equivalent to the dicarboxylic acid component monomer. Is volatile, add at least an equivalent to the dicarboxylic acid component monomer, sulfuric acid,
It can be synthesized by transesterification by heating using an inorganic acid such as phosphoric acid, an acetate or carbonate such as titanium alkoxide, calcium and cobalt, or an oxide of zinc or lead as a catalyst. When the diol component monomer is volatile, 2 equivalents per 1 equivalent of the dicarboxylic acid component monomer is used.
１００100 equivalents, preferably 3-50 equivalents.
The catalyst was used in an amount of 1 part by weight based on 1 part by weight of the produced polyester.
/ 1000-1 part by weight, preferably 1 / 1000-1
/ 2 parts by weight. The reaction is performed at a reaction temperature of 200 to 3
The reaction is carried out at 00 ° C.
The reaction is preferably performed under reduced pressure to about mmHg, preferably 0.05 to 20 mmHg. Alternatively, the reaction may be carried out using a high-boiling solvent such as 1-chloronaphthalene, which can be azeotropic with the diol component monomer, while azeotropically removing the diol component monomer under normal pressure.

Among these synthesis methods, the method (3) is the most preferable because a high molecular weight polyester is easily obtained.
If the polymerization degree p of the charge transporting polyester is too low, the film formability is poor and a strong film is hardly obtained. On the other hand, if the polymerization degree p is too high, the solubility in a solvent becomes low and the processability deteriorates.
Used in the range of ~ 500, preferably 10 ~ 300,
More preferably, it is set to 15 to 100. The weight average molecular weight (GPC method: styrene conversion) is 10,000
0 to 300,000, preferably 15,000 to 200,000, more preferably 50,000 to 1
It is set in the range of 00,000. Further, in the structures represented by the formulas A and A ′, k represents an integer selected from 0 or 1, and when k is 1, the charge distribution in the charge transport component is less likely to be biased, and high transportability is obtained. It is preferable because it can be obtained.

The present invention can be applied to the charge-transporting polyester, the electrophotographic photoreceptor or the organic electroluminescent device of the present invention, and may be used alone, or may contain an insulating polymer compatible therewith. You may.

Specifically, a device having a structure in which a layer containing the above-described charge transporting polyester is provided on a support is used as an organic electronic device. Representative examples of the organic electronic device include an electrophotographic photoreceptor having a photosensitive layer, and in particular, those containing the charge transporting polyester of the present invention in a surface layer of the electrophotographic photoreceptor. . The photosensitive layer containing the charge-transporting polyester of the present invention as a charge-transporting material and a known charge-generating material, in particular, an electrophotographic photosensitive member containing a phthalocyanine compound crystal is preferable.

In the electrophotographic photoreceptor of the present invention, the phthalocyanine crystal used in combination with the charge transporting polyester is described in JP-A-5-98181.
Gallium phthalocyanine crystal disclosed in JP-A-5-140472 and JP-A-5-140472
Halogenated tin phthalocyanine crystal disclosed in JP-A-140473, hydroxygallium phthalocyanine crystal disclosed in JP-A-5-263007 and JP-A-5-279951, JP-A-4-189
No. 873 and Japanese Patent Application Laid-Open No. 5-43813, oxytitanium phthalocyanine hydrate crystals are disclosed.
An electrophotographic photosensitive member having excellent repetition stability can be obtained.

As disclosed in JP-A-5-98181, chlorogallium phthalocyanine crystals used in the present invention are prepared by converting a chlorogallium phthalocyanine crystal produced by a known method into an automatic mortar, a planetary mill, and a vibrator. It can be manufactured by mechanically dry-pulverizing with a mill, CF mill, roller mill, sand mill, kneader, or the like, or by performing dry pulverization, followed by wet pulverization with a solvent using a ball mill, mortar, sand mill, kneader, or the like. .
Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), and aliphatic polyhydric alcohols. Alcohols (ethylene glycol, glycerin,
Polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.) And a mixture of several kinds, and a mixture of water and these organic solvents. The solvent used is used in an amount of 1 to 200 parts, preferably 10 to 100 parts, based on chlorogallium phthalocyanine. The treatment temperature is in the range of 0 ° C. to the boiling point of the solvent or lower, preferably 10 to 60 ° C.
Further, at the time of pulverization, a grinding aid such as salt and sodium nitrate can be used. The grinding aid may be used 0.5 to 20 times, preferably 1 to 10 times the pigment.

Dichlorotin phthalocyanine crystals are disclosed in JP-A-5-140472 and JP-A-5-14047.
As disclosed in Japanese Patent Publication No. 3 (1993) -313, dichlorotin phthalocyanine crystals produced by a known method can be obtained by pulverizing and treating with a solvent in the same manner as the above-mentioned chlorogallium phthalocyanine.

Hydroxygallium phthalocyanine crystals are disclosed in JP-A-5-263007 and JP-A-5-252.
As disclosed in JP 795991, chlorogallium phthalocyanine crystals produced by a known method are subjected to hydrolysis or acid pasting in an acid or alkaline solution to synthesize hydroxygallium phthalocyanine crystals, Solvent treatment, or
The hydroxygallium phthalocyanine crystal obtained by the synthesis is subjected to a wet milling treatment using a ball mill, a mortar, a sand mill, a kneader or the like with a solvent, or a dry milling treatment without using a solvent followed by a solvent treatment. Can be. Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), Polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetate,
Examples thereof include butyl acetate, ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.), a mixture of several kinds, and a mixture of water and these organic solvents. The solvent used is 1 to 200 parts, preferably 10 to 100 parts, based on hydroxygallium phthalocyanine.
Used in the range of parts. The processing temperature is in the range of 0 to 150 ° C, preferably room temperature to 100 ° C. Further, at the time of pulverization, a grinding aid such as salt and sodium nitrate can be used. The grinding aid is used in the range of 0.5 to 20 times, preferably 1 to 10 times the pigment.

The oxytitanium phthalocyanine crystal is
JP-A-4-189873 and JP-A-5-4381
No. 3, as disclosed in Japanese Patent Publication No. 3, oxytitanium phthalocyanine crystal produced by a known method, acid pasting, or ball mill, mortar,
Salt milling was performed together with the inorganic salt using a sand mill, a kneader, or the like, and the X-ray diffraction spectrum was 27.
After the oxytitanium phthalocyanine crystal having relatively low crystallinity having a peak at 2, a direct solvent treatment is performed, or a wet grinding treatment is performed using a ball mill, a mortar, a sand mill, a kneader or the like together with the solvent. Can be manufactured. As the acid used for acid pasting, sulfuric acid is preferable, and the concentration is 70 to 100.
%, Preferably 95 to 100%, and the dissolution temperature is set in the range of -20 to 100C, preferably 0 to 60C. The amount of concentrated sulfuric acid is set in the range of 1 to 100 times, preferably 3 to 50 times, the weight of the oxytitanium phthalocyanine crystal. As a solvent to be precipitated, water or a mixed solvent of water and an organic solvent is used in an arbitrary amount, and water and an alcoholic solvent such as methanol and ethanol, or a mixture of water and an aromatic solvent such as benzene and toluene are used. Solvents are particularly preferred. The temperature for the precipitation is not particularly limited, but is preferably cooled with ice or the like in order to prevent heat generation. The ratio between the oxytitanium phthalocyanine crystal and the inorganic salt is from 1 / 0.1 by weight.
1/20, preferably in the range of 1 / 0.5 to 1/5. Solvents used in the above solvent treatment include aromatics (toluene, chlorobenzene, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), halogenated hydrocarbons (dichloromethane, chloroform, trichloroethane, etc.), and furthermore Is a mixed system of several kinds, a mixed system of water and these organic solvents, and the like. The solvent used is
1 to 100 relative to oxytitanium phthalocyanine
Times, preferably 5 to 50 times. The processing temperature is set in the range of room temperature to 100 ° C, preferably 50 to 100 ° C. The grinding aid is 0.5 to 20 times the pigment,
Preferably, it may be used 1 to 10 times.

Next, the electrophotographic photosensitive member will be described.
As the conductive support, metals such as aluminum, nickel, chromium, and stainless steel, and plastics provided with thin films of aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, ITO, and the like Examples include films and the like, or paper and plastic films coated or impregnated with a conductivity imparting agent. These conductive supports are used in an appropriate shape such as a drum shape, a sheet shape, and a plate shape, but are not limited thereto. Further, if necessary, the surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, oxidation treatment, chemical treatment, coloring treatment, or the like, or irregular reflection treatment such as graining can be performed on the surface. Further, an undercoat layer may be further provided between the conductive support and the charge generation layer. The undercoating layer prevents the injection of electric charge from the conductive support to the photosensitive layer when the photosensitive layer having the laminated structure is charged, and also bonds the photosensitive layer integrally to the conductive support. It acts as a layer or, in some cases, acts as an anti-reflection of light on the conductive support.

As the binder used for the undercoat layer, polyethylene resin, polypropylene resin, acrylic resin,
Methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester Resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, titanium chelate compound,
Known materials such as titanium alkoxide compounds, organic titanium compounds, and silane coupling agents can be used. The thickness of the undercoat layer is suitably from 0.01 to 10 μm, preferably from 0.05 to 2 μm. Further, as an application method used when providing the undercoat layer, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, etc. Can be used.

For the charge transport layer, the charge transport polyester of the present invention may be used alone, or a known binder resin, another hydrazone charge transport material, a triarylamine charge transport material, or a stilbene charge transport material may be used. You may use together with a material etc. When using a binder resin, specifically, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride -Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicon-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N- Known resins such as vinyl carbazole and polysilane can be used, but are not limited thereto. Among these binder resins, the following structural formula (XI)
~ (XVI) polycarbonate resin, and
When a polycarbonate resin obtained by copolymerizing them is used, good compatibility is obtained, a uniform film is obtained, and particularly good characteristics are exhibited. The compounding ratio (weight ratio) is preferably in the range of charge transporting polyester: binder resin = 10: 0 to 8:10. Also,
When mixed with another charge transporting material, charge transporting polyester + binder resin: charge transporting material = 10: 0 to 10:
A range of 8 is preferred. The thickness of the charge transport layer is 5 to 5
0 μm, preferably 10 to 40 μm is suitable. Further, as an application method used when providing the charge transport layer, a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method,
Bead coating method, air knife coating method,
An ordinary method such as a curtain coating method can be used.

[0053]

Embedded image (Where n is a polymerization degree of 50 to 3,000)

For the charge generation layer, it is preferable to use the above-mentioned phthalocyanine crystal as the charge generation material. Can be used.

The binder resin used for the charge generation layer can be selected from a wide range of insulating resins. Further, poly-N-vinyl carbazole, polyvinyl anthracene,
It can also be selected from organic photoconductive polyesters such as polyvinylpyrene and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin And insulating resins such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin and polyvinyl pyrrolidone resin, but are not limited thereto. These binder resins can be used alone or in combination of two or more.

The compounding ratio (weight ratio) of the charge generating material to the binder resin is preferably in the range of 10: 1 to 1:10.
As a method for dispersing these, a usual method such as a ball mill dispersion method, an attritor dispersion method, and a sand mill dispersion method can be used. Further, at the time of this dispersion, it is effective that the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, and more preferably 0.15 μm or less. The solvents used for these dispersions include methanol, ethanol, n-propanol, and n-propanol.
Butanol, benzyl alcohol, methyl cellosolve,
A common organic solvent such as ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in combination of two or more. . The thickness of the charge generation layer is suitably from 0.01 to 10 μm, preferably from 0.05 to 5 μm. Further, as an application method used when providing the charge generation layer, a usual method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like. Can be used.

[0057]

The present invention will be described below by way of examples. For example, a monomer used for producing a charge transporting polyester can be synthesized as follows. Synthesis Example 1 N, N-bis (3- (2- (ethoxycarbonyl) ethyl) phenyl) -3,4-xylysine (partial structure of (I
Synthesis of 3,4-xylysine 6 g, ethyl 3-iododihydrocinnamate 34 g, potassium carbonate 19 g, copper sulfate pentahydrate 5
g and 20 ml of n-tridecane were placed in a 1000 ml flask, and heated and reacted at 230 ° C. for 10 hours under a nitrogen stream.
After the reaction, the mixture was cooled to room temperature, dissolved in 500 ml of toluene, insolubles were filtered, and the filtrate was produced by silica gel column chromatography using toluene. 20 g of oily N, N-bis (3- (2- (ethoxycarbonyl) ethyl) phenyl) -3,4-xylysine was obtained.

Synthesis Example 2 N, N'-diphenyl-N, N'-bis (3- (2-
(Ethoxycarbonyl) ethyl) phenyl)-[1,
Synthesis of 1'-biphenyl] -4,4'-diamine (partial structure is represented by (I-6) and both ends are ethyl esters) N, N'-diphenylbenzidine 10.77 g, 3-iododihydrocinnamic acid 23.0 g of ethyl, 11.61 g of potassium carbonate, 1.0 g of copper sulfate pentahydrate, and 20 ml of n-tridecane were placed in a 100 ml flask, and heated and reacted at 230 ° C. for 1 hour in a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 50 ml of toluene, the insoluble matter was filtered, and the filtrate was produced by silica gel column chromatography using toluene. 19.6 g of oily N, N'-diphenyl-N, N'-bis (3- (2- (ethoxycarbonyl) ethyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine was obtained. Was.

Synthesis Example 3 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[ 1,1'-biphenyl] -4,4'-diamine (partial structure of (I-19)
Wherein both ends are methyl esters) N- (3,4-dimethylphenyl) -N- (4- (2-
(Methoxycarbonyl) ethyl) phenyl) amine 45
g, 4,4'-diiodo-3,3'-dimethylbiphenyl, 30 g of potassium carbonate, 5 g of copper sulfate pentahydrate,
20 ml of n-tridecane was placed in a 1000 ml flask, and heated and reacted at 230 ° C. for 5 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 200 ml of toluene,
The insolubles were filtered, the filtrate was purified by silica gel column chromatography using toluene, and recrystallized from a mixed solvent of ethyl acetate and ethanol to give 3,3′-dimethyl-N,
N'-bis (3,4-dimethylphenyl) -N, N'-
38 g of bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine was obtained as a pale yellow powder (melting point: 161.5
１６163 ° C.).

Synthesis Example 4 3,3'-dimethyl-N, N'-bis (4-methoxyphenyl) -N, N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1, Synthesis of 1'-biphenyl] -4,4'-diamine (the partial structure is represented by (I-22) and both terminals are methyl esters) N- (4-methoxyphenyl) -N- (4- (2- (Methoxycarbonyl) ethyl) phenyl) amine 5.0
g, 3.4 g of 4,4'-diiodo-3,3'-dimethylbiphenyl, 2.9 g of potassium carbonate, 0.5 g of copper sulfate pentahydrate, and 5 ml of n-tridecane were placed in a 100 ml flask and placed under a nitrogen stream. The reaction was carried out at 230 ° C. for 15 hours. After the reaction, the mixture was cooled to room temperature, dissolved in 20 ml of toluene, insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene. 3,3'-dimethyl-N, N'-bis (4-methoxyphenyl) -N, N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1 ' -Biphenyl] -4,4'-diamine (5.3 g) was obtained.

Synthesis Example 5 N, N'-bis (3,4-dimethylphenyl) -N,
N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1 ': 4', 1 "-terphenyl] -4,4" -diamine (partial structure of (I-31) Wherein both ends are methyl esters) N- (3,4-dimethylphenyl) -N- (4- (2-
(Methoxycarbonyl) ethyl) phenyl) amine5.
0 g, 4,4 "-diiodo- [1,1 ': 4', 1"-
Terphenyl] 3.8 g, potassium carbonate 2.9 g, copper sulfate pentahydrate 1.0 g, n-tridecane 10 ml
The mixture was placed in a flask having a capacity of 200 ml and heated at 230 ° C. for 5 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, and toluene 20m
l, the insolubles are filtered, the filtrate is purified by silica gel column chromatography using toluene, and recrystallized from acetone to give N, N'-bis (3,4-dimethylphenyl) -N , N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1 ': 4', 1 "
3.7 g of (-terphenyl) -4,4 ″ -diamine was obtained as a pale yellow powder (melting point: 146 to 147 ° C.).

Synthesis Example 6 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis ((4-methoxycarbonylmethyl) phenyl)-[1,1 ' -Biphenyl]-
Synthesis of 4,4'-diamine (the partial structure is represented by (I-18) and both terminals are methyl esters) N- (3,4-dimethylphenyl) -N- (4- (2-
Methoxycarbonylmethyl) phenyl) amine 9.0
g, 4,4'-diiodo-3,3'-dimethylbiphenyl, 6.2 g, potassium carbonate 5.5 g, copper sulfate pentahydrate 1.0 g, and n-tridecane 10 ml were placed in a 200 ml flask and placed under a nitrogen stream. The reaction was carried out by heating at 230 ° C. for 5 hours. After the reaction, the solution was cooled to room temperature, dissolved in 40 ml of toluene, insolubles were filtered, and the filtrate was purified by silica gel column chromatography using toluene. Recrystallized from a mixed solvent of ethyl acetate and ethanol to give 3,3 '
-Dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis (4- (2-methoxycarbonylmethyl) phenyl)-[1,1'-biphenyl] -4,
7.1 g of 4'-diamine was obtained as a pale yellow powder (melting point: 179-181 ° C).

Synthesis Example 7 N, N'-diphenyl-N, N'-bis (4- (4-
Synthesis of (2- (ethoxycarbonyl) ethyl) phenyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine (a partial structure is represented by (I-52) and both terminals are ethyl esters) N, N'-diphenylbenzidine 1
0.0 g, 4- (2- (ethoxycarbonyl) ethyl)
-4'-iodobiphenyl 24.0 g, potassium carbonate 1
1 g, copper sulfate pentahydrate 1.0 g, n-tridecane 30 m
1 into a 200 ml flask and placed under a nitrogen stream at 230 ° C.
For 1 hour. After the reaction, the mixture was cooled to room temperature, dissolved in 10 ml of toluene, insolubles were filtered, and the filtrate was produced by silica gel column chromatography using toluene. Oily N, N'-diphenyl-N, N'-bis (4
-(4- (2- (ethoxycarbonyl) ethyl) phenyl) phenyl)-[1,1'-biphenyl] -4,4 '
-16.6 g of diamine were obtained.

Synthesis Example 8 N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4-amine (partial structure is represented by (I-2), and both terminals are methyl esters) Synthesis of N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) amine 25.0 g, 4-iodobiphenyl 20.5 g, potassium carbonate 12.0 g, copper sulfate pentahydrate 1.0 g, 30 ml of n-tridecane was placed in a 200 ml flask, and heated and reacted at 230 ° C. for 3 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 100 ml of toluene, insolubles were filtered, and the filtrate was produced by silica gel column chromatography using toluene. After recrystallization from a mixed solvent of acetone and ethanol, N, N-bis (4
-(2- (methoxycarbonyl) ethyl) phenyl)-
24.5 g of biphenyl-4-amine was obtained as a pale yellow powder (melting point: 92-93 ° C.).

Synthesis Example 9 1,2-bis (4- (N- (4- (2- (methoxycarbonyl) ethyl) phenyl) -N- (4-phenylphenyl) amino) phenyl) ethane (partial structure of ( I-4
Synthesis of N- (4- (2- (methoxycarbonyl) ethyl) phenyl) -N- (4-phenylphenyl) amine 5.0
g, 1,2-bis (4-iodophenyl) ethane 3.0
g, potassium carbonate 2.1 g, copper sulfate pentahydrate 0.2 g,
10 ml of n-tridecane was placed in a 100 ml flask, and heated and reacted at 230 ° C. for 3 hours under a nitrogen stream. After the reaction, the mixture was cooled to room temperature, dissolved in 10 ml of toluene, insolubles were filtered, and the filtrate was produced by silica gel column chromatography using toluene. After recrystallization from a mixed solvent of acetone and ethanol, 1,2-bis (4- (N- (4
-(2- (methoxycarbonyl) ethyl) phenyl)-
3.6 g of N- (4-phenylphenyl) amino) phenyl) -ethane was obtained as a pale yellow powder (melting point: 157).
-159 ° C).

Synthesis Example 10 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis (4- (2- (hydroxyethyl) phenyl))-[1 , 1'-biphenyl]-
Synthesis of 4,4'-diamine (the partial structure is represented by (II-18) and both terminals are hydroxyl groups) 3,3'-dimethyl-N, N'- synthesized in Synthesis Example 6
Bis (3,4-dimethylphenyl) -N, N'-bis ((4-methoxycarbonylmethyl) phenyl)-
[1,1′-biphenyl] -4,4′-diamine10.
0 g and 50 ml of tetrahydrofuran were placed in a 100 ml flask and dissolved, and 1.2 g of lithium aluminum hydride was gradually added to this solution. After the reaction was completed, methanol and water were added to consume excess lithium aluminum hydride, and the purified precipitate was filtered. Water was further added to the filtrate, extraction was performed with toluene, and the toluene phase was sufficiently washed with water. This was dried over sodium sulfate and recrystallized from ethyl acetate and methanol to give 3,3'-dimethyl-
N, N'-bis (3,4-dimethylphenyl) -N,
7.0 g of N'-bis (4- (2- (hydroxyethyl) phenyl))-[1,1'-biphenyl] -4,4'-diamine were obtained (melting point: 214-216 ° C.).

Synthesis Example 11 3,3′-dimethyl-N, N′-bis (3,4-dimethylphenyl) -N, N′-bis (4- (3- (hydroxypropyl) phenyl))-[1 , 1'-biphenyl]
Synthesis of -4,4'-diamine (partial structure is represented by (II-19) and both terminals are hydroxyl groups) 3,3'-dimethyl-N, N'- synthesized in Synthesis Example 3
10.0 g of bis (3,4-dimethylphenyl) -N, N'-bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1'-biphenyl] -4,4'-diamine Except for using, in the same manner as in Synthesis Example 10,
3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis (4- (3- (hydroxypropyl) phenyl))-[1,1'-biphenyl]
7.2 g of -4,4'-diamine was obtained (melting point: 182
１８184 ° C.).

Synthesis Example 12 N, N'-diphenyl-N, N'-bis (4- (4-
(2- (hydroxyethyl) phenyl) phenyl)-
Synthesis of [1,1'-biphenyl] -4,4'-diamine (partial structure is represented by (II-52) and both terminals are hydroxyl groups) N, N'-diphenyl-N synthesized in Synthesis Example 7 , N '
-Bis (4- (4- (2- (ethoxycarbonyl) ethyl) phenyl) phenyl)-[1,1'-biphenyl]
N, N'-diphenyl-N, N 'in the same manner as in Synthesis Example 10 except that 10.0 g of -4,4'-diamine was used.
-Bis (4- (4- (2- (hydroxyethyl) phenyl) phenyl)-[1,1'-biphenyl] -4,4 '
6.5 g of diamine were obtained (melting point: 143-145).
° C).

Synthesis Example 13 30 parts of 1,3-diiminoisoindoline and 9.1 parts of gallium trichloride were placed in 230 parts of quinoline and reacted at 200 ° C. for 3 hours. ,
After washing with methanol and then drying the wet cake,
28 parts of chlorogallium phthalocyanine crystals were obtained. 3 parts of the obtained chlorogallium phthalocyanine crystal was dry-pulverized in an automatic mortar (Lab-Mill UT-21 type, manufactured by Yamato Scientific Co., Ltd.) for 3 hours, and 0.5 part together with 60 parts of glass beads (1 mmφ) at room temperature. After milling in 20 parts of benzyl alcohol for 24 hours, the glass beads were filtered off, washed with 10 parts of methanol and dried, and the powder X-ray diffraction spectrum showed 2θ ± 0.2 ° = 7.4 °, 1
A chlorogallium phthalocyanine crystal having strong diffraction peaks at 6.6 °, 25.5 ° and 28.3 ° was obtained. This is designated as CG-1.

Synthesis Example 14 50 g of phthalonitrile and 27 g of anhydrous stannic chloride
Was added to 350 ml of 1-chloronaphthalene, and 195
After reacting at 5 ° C. for 5 hours, the product was filtered off,
After washing with chlornaphthalene, acetone, methanol and then water, drying was performed under reduced pressure to obtain 18.3 g of dichlorotin phthalocyanine crystals. 5 g of the obtained dichlorotin phthalocyanine crystal was mixed with 10 g of salt and agate ball (20 g).
mmφ) 500 g together with an agate pot and 400 in a planetary ball mill (P-5, Fritsch)
After pulverizing at rpm for 10 hours, the resultant was sufficiently washed with water and dried. 0.5 g of the mixture was added to 15 g of THF and glass beads (1
After milling at room temperature for 24 hours together with 30 g of glass beads, the glass beads were filtered off, washed with methanol and dried, and the powder X-ray diffraction spectrum showed 2θ ± 0.2 ° =
Dichlorotin phthalocyanine crystals having strong diffraction peaks at 8.5 °, 11.2 °, 14.5 ° and 27.2 ° were obtained. This is designated as CG-2.

Synthesis Example 15 3 parts of the chlorogallium phthalocyanine crystal obtained in Synthesis Example 3 was dissolved in 60 parts of concentrated sulfuric acid at 0 ° C., and the above solution was added dropwise to 450 parts of 5 ° C. distilled water to recrystallize the crystal. Was deposited.
After washing with distilled water, dilute ammonia water, etc., and drying,
Five parts of hydroxygallium phthalocyanine crystals were obtained.
The crystals were ground in an automatic mortar for 5.5 hours, and
After milling 5 parts with 15 parts of dimethylformamide and 30 parts of glass beads having a diameter of 1 mm for 24 hours, the crystals were separated, washed with methanol and dried, and the powder X-ray diffraction spectrum showed 2θ ± 0.2 ° = 7.5 °. , 9.9 °, 12.5
°, 16.3 °, 18.6 °, 25.1 ° and 28.3
A hydroxygallium phthalocyanine crystal having a strong diffraction peak at ° was obtained. This is designated as CG-3.

Synthesis Example 16 30 parts of 1,3-diiminoisoindoline and 17 parts of titanium tetrabutoxide were placed in 200 parts of 1-chloronaphthalene, reacted at 190 ° C. for 5 hours under a nitrogen stream, and the product was filtered. Then, the resultant was washed with aqueous ammonia, water and acetone to obtain 40 parts of oxytitanium phthalocyanine. 5 parts of the obtained oxytitanium phthalocyanine crystal and 10 parts of sodium chloride were placed in an automatic mortar (Lab-MILL).
(UT-21, manufactured by Yamato Scientific Co., Ltd.) for 3 hours. Then, it was sufficiently washed with distilled water and dried to obtain 4.8 parts of oxytitanium phthalocyanine crystals. The obtained oxytitanium phthalocyanine crystal showed a clear peak at 2θ ± 0.2 ° = 27.3 ° in the powder X-ray diffraction spectrum. The obtained oxytitanium phthalocyanine crystal (2 parts) was stirred in a mixed solvent of distilled water (20 parts) and monochlorobenzene (2 parts) at 50 ° C. for 1 hour, filtered, sufficiently washed with methanol, dried, and dried with powder X-ray. An oxytitanium phthalocyanine hydrate crystal having a strong diffraction peak at 2θ ± 0.2 ° = 27.3 ° in the diffraction spectrum was obtained. This is designated as CG-4.

Example 1 N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4-synthesized in Synthesis Example 8
6.0 g (12.2 mmol) of amine, 3,3'-dimethyl-N, N'-bis (3,4-
8.37 g (12.2 mm) of dimethylphenyl) -N, N'-bis (4- (3- (hydroxypropyl) phenyl))-[1,1'-biphenyl] -4,4'-diamine
ol) and 0.1 g of tetrabutoxy titanium in 100 ml
And gradually heated to 200 ° C. over 1 hour under a nitrogen stream. When the generation of methanol was completed, the pressure was reduced to 1 mmHg, and the reaction was further performed for 2 hours. After the completion of the reaction, the mixture was cooled to room temperature, dissolved in 30 ml of methylene chloride, and insolubles were filtered. 5 ml of 1-N hydrochloric acid was added to this solution.
After stirring vigorously for 30 minutes, thoroughly washing with water, 200 ml of isopropanol was added dropwise while stirring,
The polymer was precipitated. 12. The obtained polymer is filtered, washed sufficiently with isopropanol, and dried, and then dried.
5 g of polymer were obtained. When the molecular weight was measured by GPC, it was Mw = 5.05 × 10 ⁴ (in terms of styrene). FIG. 1 shows the IR spectrum.

Example 2 N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4-synthesized in Synthesis Example 8
Amine 6.0 g, 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) synthesized in Synthesis Example 11
-N, N'-bis (4- (3- (hydroxypropyl)
Phenyl))-[1,1'-biphenyl] -4,4'-
8.37 g of diamine, 30 ml of p-cymene and 0.1 g of tetrabutoxytitanium are put in a 100 ml flask,
The mixture was heated under reflux for 4 hours under a nitrogen stream. After the completion of the reaction, the mixture was cooled to room temperature, 30 ml of methylene chloride was further added, and insolubles were filtered. 5 ml of 1-N hydrochloric acid was added to this solution,
After vigorous stirring for 30 minutes, thorough washing and water washing, 300 ml of isopropanol was added dropwise while stirring to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with isopropanol, and dried to obtain 13.8 g of a polymer. When the molecular weight was measured by GPC, M
w = 7.05 × 10 ⁴ (styrene equivalent). IR
The spectrum was similar to FIG.

Example 3 3,3'-dimethyl synthesized in Synthesis Example 3 instead of 6.0 g of N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4-amine −N,
N'-bis (3,4-dimethylphenyl) -N, N'-
Except that 9.06 g of bis (4- (2- (methoxycarbonyl) ethyl) phenyl)-[1,1′-biphenyl] -4,4′-diamine was used, 1
5.4 g of polymer were obtained. When the molecular weight was measured by GPC, it was Mw = 1.36 × 10 ⁵ (in terms of styrene). FIG. 2 shows the IR spectrum.

Example 4 N, N-bis (4- (2- (methoxycarbonyl) ethyl) phenyl) -biphenyl-4-synthesized in Synthesis Example 8
6.0 g of amine, 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl)-synthesized in Synthesis Example 11
N, N'-bis (4- (3- (hydroxypropyl) phenyl))-[1,1'-biphenyl] -4,4'-diamine (7.8 g), ethylene glycol (1.0 g) and tetrabutoxytitanium 0 0.1 g was placed in a 100 ml flask, and the temperature was gradually raised to 200 ° C. over 1 hour under a nitrogen stream. Then, the pressure was reduced to 1 mmHg,
Reacted for hours. After the completion of the reaction, the mixture was cooled to room temperature, dissolved in 30 ml of methylene chloride, and insolubles were filtered. To this solution was added 5 ml of 1-N hydrochloric acid, and the mixture was vigorously stirred for 30 minutes. After thoroughly washing with water, 200 ml of isopropanol was dropped into the solution while stirring to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with isopropanol, and then dried to obtain 12.3 g of a polymer. When the molecular weight was measured by GPC, Mw = 8.05 × 10
⁴ (styrene equivalent).

Examples 5 to 15 Polymers were synthesized in the same manner as in Example 1 except that the combinations of dicarboxylic acid esters and diols were as shown in Table 1, and that each of the dicarboxylic acid esters and diols was used in an amount of 12.2 mmol. Table 15 shows the results.

[0078]

[Table 15]

Comparative Example 1 3,3'-dimethyl-N, N'-bis (3,4-dimethylphenyl) -N, N'-bis [4
-(2-methoxycarbonylethyl) phenyl]-
[1,1′-biphenyl] -4,4′-diamine 15.
0 g, 3.0 g of dimethyl terephthalate, 30.0 g of ethylene glycol and 0.1 g of tetrabutoxytitanium were placed in a 300 ml flask, and heated and refluxed for 3 hours under a nitrogen stream. 3,3'-dimethyl-N, N'-bis (3,
4-dimethylphenyl) -N, N'-bis [4- (2-
Methoxycarbonylethyl) phenyl]-[1,1′-
After confirming that [biphenyl] -4,4'-diamine was consumed, the pressure was reduced to 0.5 mmHg, and the mixture was heated to 235 ° C while distilling off ethylene glycol, and the reaction was continued for 2.5 hours. Thereafter, the mixture was cooled to room temperature, and methylene chloride 20
0 ml, and the insoluble material was filtered.
400 ml was added dropwise while stirring to precipitate a polymer. The obtained polymer was filtered, sufficiently washed with ethanol, and then dried to obtain 17.0 g of a polymer. When the molecular weight was measured by GPC, Mw = 1.4.
It was 0 × 10 ⁵ (styrene equivalent).

Comparative Example 2 A polymer was synthesized in the same manner as in Comparative Example 1 except that dimethyl sebacate was used instead of dimethyl terephthalate. Comparative Example 3 Comparative Example 1 except that dimethyl terephthalate was not added.
A polymer was synthesized in the same manner as described above.

Example 16 A zirconium compound (trade name: Olgatics ZC) was placed on a honing-treated 20 mmφ stainless steel cylindrical substrate.
540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and a solution consisting of 10 parts of a silane compound (trade name: A1110, manufactured by Japan Junker Co., Ltd.), 400 parts of i-propanol and 200 parts of butanol, are applied by dip coating, and then applied at 150 ° C. The coating was dried by heating for 0.5 minute to form an undercoat layer having a thickness of 0.5 μm. 10 parts of CG-1 was used as a polyvinyl butyral resin (trade name: S-LEC BM-S, manufactured by Sekisui Chemical Co., Ltd.) 1
After mixing with 0 parts and 500 parts of n-butyl acetate and treating with a glass shaker for 1 hour with a paint shaker and dispersing, the obtained coating solution was applied on the undercoat layer by a dip coating method, Heat drying for 10 minutes. 5 parts of the charge transporting polymer obtained in Example 1 was dissolved in 38 parts of monochlorobenzene, and the obtained coating solution was applied on a stainless steel cylindrical substrate on which a charge generation layer was formed by dip coating. Heat drying at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 23 μm.

The electrophotographic characteristics of the thus obtained electrophotographic photoreceptor were measured using a laser beam printer test model-1 (A-4 in the horizontal direction, 1 minute per minute) manufactured by Fuji Xerox Co., Ltd.
(2 sheets), a print test was performed under a normal environment (20 ° C., 50% RH), and the image quality after the first sheet and after copying 2,000 sheets was evaluated. The light amount was adjusted using a filter depending on the sensitivity of the charge generation material. Table 16 shows the results.

Examples 17 to 30, Comparative Examples 4 to 6 Electrophotographic photosensitive members were prepared and evaluated in the same manner as in Example 4, except that the combinations of the charge generating materials and the charge transporting polymers were changed as shown in Table 16. Table 16 shows the results.

[0084]

[Table 16]

[0085]

The charge-transporting polyester of the present invention is a novel substance and can be easily obtained as a high-molecular-weight polymer, as is clear from the results of the above-mentioned examples. It is a useful material for organic electronic devices such as photoreceptors. The electrophotographic photoreceptor using the charge transporting polyester of the present invention has good sensitivity and excellent repetition stability.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of a charge transporting polyester synthesized in Example 1.

FIG. 2 is an IR spectrum of the charge transporting polyester synthesized in Example 3.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Rie Ishii 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. Reference) 2H068 AA02 AA19 AA20 AA21 BA39 BB23 BB49 BB52 4J029 AA03 AB01 AD01 AD10 AE18 BB18 BC07A BC07B BC09 BH01 CB14A CC09 CH01 DA06 DA14

Claims (8)

[Claims] 1. A dicarboxylic acid component comprising at least one or more structures represented by the following general formula (I) and a diol component comprising at least one or more structures represented by the following general formula (II). A charge-transporting polyester, which is contained as a partial structure of a repeating unit. -CO- (T) a-A- (T) a-CO- (I) -O- (T) b-A '-(T) b-O- (II) wherein A and A' are And a divalent group represented by the following formula. Embedded image (R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
X represents a halogen atom, an alkyl group, an alkoxy group, or a substituted or unsubstituted aryl group, and X represents a substituted or unsubstituted divalent organic group. a, b, k and m each represent an integer of 0 or 1, and T represents a divalent hydrocarbon group having 1 to 10 carbon atoms which may be branched. )] 2. A weight average molecular weight of 10,000 to 30.
The charge-transporting polyester according to claim 1, which has a molecular weight of 000. 3. The charge according to claim 1, wherein the dicarboxylic acid component comprises only the structure represented by the general formula (I), and the diol component comprises only the structure represented by the general formula (II). Transportable polyester. 4. The charge transporting polyester according to claim 1, wherein the group X is a biphenylene group, a 3,3′-dimethylbiphenylene group or a terphenylene group. 5. An organic electronic device comprising the charge-transporting polyester according to any one of claims 1 to 4 in a charge-transporting functional film. 6. The organic electronic device according to claim 5, wherein the organic electronic device comprises an electrophotographic photosensitive member having a photosensitive layer. 7. The organic electronic device according to claim 5, wherein the charge transporting polyester according to any one of claims 1 to 4 is contained in a surface layer of an electrophotographic photosensitive member. 8. An organic electronic device comprising an electrophotographic photoreceptor having a photosensitive layer, wherein the charge transporting material in the photosensitive layer comprises the charge transporting polyester according to claim 1; 8. The organic electronic device according to claim 5, wherein a gallium phthalocyanine halide crystal, a halogenated tin phthalocyanine crystal, a hydroxygallium phthalocyanine crystal or an oxytitanium phthalocyanine crystal is contained as a generating material.